WO2024005030A1 - Diphenylethene-based compound, light absorber, resin composition, and use thereof - Google Patents

Abstract

A diphenylethene-based compound according to the present invention is represented by formula (I).

Description

Diphenylethene compounds, light absorbers, resin compositions and their uses

The present invention relates to diphenylethene compounds, light absorbers, resin compositions, and uses thereof.

As blue LED elements become more efficient and their prices fall, lighting with LED light sources, displays for LCD TVs and personal computers that use LED light sources for backlighting, portable electronic devices, automobile lights that use LED light sources, etc. is increasing. These lights contain more blue components than conventional light sources, and as a result, we are more likely to experience glare than before. In recent years, in order to alleviate the discomfort, visual fatigue, etc. associated with this, it has been known to add a light absorbing agent to spectacle lenses and the like to impart an anti-glare function (Reference 1).

Additionally, optical filters used to improve the visibility of various display devices such as liquid crystal displays are required not only to have ultraviolet to blue light cutting performance, but also to have excellent visible light transparency and light resistance. Furthermore, as a technology related to contrast properties, an optical filter having an absorption maximum in a wavelength region of 380 to 420 nm, a wavelength region of 480 to 520 nm, and a wavelength region of 585 nm to 620 nm has been disclosed (Reference 2).

Among ultraviolet to blue light, light in the blue to violet region of 450 nm or less is perceived as more dazzling, so light absorbers are added to cut light in this wavelength range, and various organic dyes, such as , squarylium compounds (Reference 3), triazole compounds (Reference 4), and diphenylethene compounds (Reference 5, Reference 6) have been investigated.

Japanese Patent Application Publication No. 2000-75128 JP2008-203436A JP2009-139911A Japanese Patent Application Publication No. 2004-352829 Japanese Unexamined Patent Publication No. 167343/1983 JP2021-24840A

Since light in the blue to violet region with a wavelength of 450 nm or less is perceived as more dazzling, various light absorbers are being studied for the purpose of cutting light in this wavelength range. However, when a resin composition containing a light absorber is continuously irradiated with light for a long period of time, the light absorber decomposes, the ability to cut light at wavelengths of 450 nm or less decreases, and visible transparency deteriorates. Issues still remained, including problems that occurred. Therefore, in recent years, there has been a demand for light absorbers that have a high ability to cut light with a wavelength of 450 nm or less and also have high durability against light and heat.

The present invention was made in view of this situation, and includes a diphenylethene-based compound as a light absorber, which efficiently absorbs light in the blue to violet region and has high light resistance, and the light absorber. An object of the present invention is to provide a resin composition.

As a result of intensive study on the above-mentioned problem, the present inventors discovered that a specific diphenylethene-based compound satisfies the above-mentioned characteristics, and completed the present invention.
That is, according to the present invention, the following technology is provided.

（式（Ｉ）中、Ｒ_１～Ｒ_１０はそれぞれ独立に、
水素原子、ハロゲン原子、シアノ基、スルホン基、
置換もしくは無置換のアルキル基、
置換もしくは無置換のアルケニル基、
置換もしくは無置換のアルキニル基、
置換もしくは無置換のアラルキル基、
置換もしくは無置換のアリール基、
置換もしくは無置換のアルキルカルボニル基、
置換もしくは無置換のアリールカルボニル基、
置換もしくは無置換のカルボン酸エステル基、
置換もしくは無置換のスルホン酸エステル基、
－ＳＲ、－ＯＲ、または－ＮＲＲ’を表す。
（式中、Ｒ及びＲ’はそれぞれ独立に、水素原子、
置換もしくは無置換の炭素数２以上のアルキル基、
置換もしくは無置換のアルケニル基、
置換もしくは無置換のアルキニル基、
置換もしくは無置換のアラルキル基、または
置換もしくは無置換のアリール基
を表す。）
Ｒ_１～Ｒ_１０は互いに結合して脂肪族環あるいは芳香環を形成しても良い。
ただし、Ｒ_１～Ｒ_１０の少なくとも１つは－ＳＲを表す。
　Ｒ_１１およびＲ_１２は、それぞれ独立に、
ハロゲン原子、シアノ基、ニトロ基、ホルミル基、カルボキシ基、スルホン基、
置換もしくは無置換のアルキル基、
置換もしくは無置換のアルケニル基、
置換もしくは無置換のアルキニル基、
置換もしくは無置換のアラルキル基、
置換もしくは無置換のアリール基、
置換もしくは無置換のアルキルカルボニル基、
置換もしくは無置換のアリールカルボニル基、
置換もしくは無置換のアリールスルホニル基、
置換もしくは無置換のカルボン酸エステル基、または
置換もしくは無置換のスルホン酸エステル基、
を表す。
Ｒ_１１～Ｒ_１２は互いに結合して脂肪族環あるいは芳香環を形成しても良い。）
［２］　前記Ｒ_１１およびＲ_１２は、それぞれ独立に、
ハロゲン原子、シアノ基、ニトロ基、ホルミル基、カルボキシ基、スルホン基、
無置換のアルキル基
置換もしくは無置換のアリール基、
置換もしくは無置換のハロゲン化アルキル基、
置換もしくは無置換のアルキルカルボニル基、
置換もしくは無置換のアリールカルボニル基、
置換もしくは無置換のアリールスルホニル基、
置換もしくは無置換のカルボン酸エステル基、または
置換もしくは無置換のスルホン酸エステル基
を表し
Ｒ_１１～Ｒ_１２は互いに結合して
置換または未置換の炭素環式脂肪族環あるいは
置換または未置換の含窒素複素環式脂肪族環を形成しても良い、
［１］に記載のジフェニルエテン系化合物。
［３］　前記Ｒ_１～Ｒ_１０は、それぞれ独立に、
水素原子、水酸基、
置換もしくは無置換の炭素数２～２０のアルキル基、
置換もしくは無置換の炭素数７～２５のアラルキル基、
置換もしくは無置換の炭素数６～２４のアリール基、
置換もしくは無置換の炭素数６～１８のアリールオキシ基、
置換もしくは無置換の炭素数２～２０のアルキルチオ基、
置換もしくは無置換の炭素数７～２５のアラルキルチオ基、または
置換もしくは無置換の炭素数６～１８のアリールチオ基
を表し、
ただし、Ｒ_１～Ｒ_１０の少なくとも１つは、
置換もしくは無置換の炭素数２～２０のアルキルチオ基、
置換もしくは無置換の炭素数７～２５のアラルキルチオ基、または
置換もしくは無置換の炭素数６～１８のアリールチオ基
を表す、［１］または［２］に記載のジフェニルエテン系化合物。
［４］　３００ｎｍ以上８００ｎｍ以下の範囲における最大吸収波長が、３００ｎｍ以上４５０以下である、［１］に記載のジフェニルエテン系化合物。
［５］　［１］に記載のジフェニルエテン系化合物を含む光吸収剤。
［６］　［１］に記載のジフェニルエテン系化合物と、樹脂と、を含む樹脂組成物。
［７］　［６］に記載の樹脂組成物からなる硬化物。
［８］　［７］に記載の硬化物からなる光学物品。 [1] A diphenylethene compound represented by the following formula (I).

(In formula (I), R ₁ to R ₁₀ are each independently,
Hydrogen atom, halogen atom, cyano group, sulfone group,
substituted or unsubstituted alkyl group,
substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group,
substituted or unsubstituted aralkyl group,
substituted or unsubstituted aryl group,
substituted or unsubstituted alkylcarbonyl group,
substituted or unsubstituted arylcarbonyl group,
substituted or unsubstituted carboxylic acid ester group,
substituted or unsubstituted sulfonic acid ester group,
-SR, -OR, or -NRR'.
(In the formula, R and R' are each independently a hydrogen atom,
Substituted or unsubstituted alkyl group having 2 or more carbon atoms,
substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group,
Represents a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group. )
R ₁ to R ₁₀ may be bonded to each other to form an aliphatic ring or an aromatic ring.
However, at least one of R ₁ to R ₁₀ represents -SR.
R ₁₁ and R ₁₂ are each independently,
Halogen atom, cyano group, nitro group, formyl group, carboxy group, sulfone group,
substituted or unsubstituted alkyl group,
substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group,
substituted or unsubstituted aralkyl group,
substituted or unsubstituted aryl group,
substituted or unsubstituted alkylcarbonyl group,
substituted or unsubstituted arylcarbonyl group,
substituted or unsubstituted arylsulfonyl group,
Substituted or unsubstituted carboxylic acid ester group, or substituted or unsubstituted sulfonic acid ester group,
represents.
R ₁₁ to R ₁₂ may be bonded to each other to form an aliphatic ring or an aromatic ring. )
[2] R ₁₁ and R ₁₂ are each independently,
Halogen atom, cyano group, nitro group, formyl group, carboxy group, sulfone group,
unsubstituted alkyl group substituted or unsubstituted aryl group,
substituted or unsubstituted halogenated alkyl group,
substituted or unsubstituted alkylcarbonyl group,
substituted or unsubstituted arylcarbonyl group,
substituted or unsubstituted arylsulfonyl group,
R ₁₁ to R ₁₂ represent a substituted or unsubstituted carboxylic acid ester group or a substituted or unsubstituted sulfonic acid ester group; may form a nitrogen heterocyclic aliphatic ring,
The diphenylethene compound according to [1].
[3] The above R ₁ to R ₁₀ are each independently,
hydrogen atom, hydroxyl group,
a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms,
a substituted or unsubstituted aralkyl group having 7 to 25 carbon atoms,
a substituted or unsubstituted aryl group having 6 to 24 carbon atoms,
a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms,
a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms,
represents a substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms,
However, at least one of R ₁ to R ₁₀ is
a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms,
The diphenylethene compound according to [1] or [2], which represents a substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms.
[4] The diphenylethene compound according to [1], which has a maximum absorption wavelength of 300 nm or more and 450 nm or less in a range of 300 nm or more and 800 nm or less.
[5] A light absorber containing the diphenylethene compound according to [1].
[6] A resin composition comprising the diphenylethene compound according to [1] and a resin.
[7] A cured product comprising the resin composition according to [6].
[8] An optical article comprising the cured product according to [7].

According to the present invention, it is possible to provide a diphenylethene compound which is a light absorbent that efficiently absorbs light in the blue to violet region and has high light resistance, and further stabilizes the absorption performance of light in the region. Resin compositions and optical articles containing the light absorbent having excellent properties can be provided.

It is a graph showing the absorbance curve of a test sample containing a diphenylethene compound in an example. It is a graph showing the light resistance test results (relationship between irradiation time and residual rate) of test samples containing diphenylethene compounds in Examples.

Hereinafter, embodiments of the present invention will be described in detail. Further, for example, "1 to 10" represents "1 or more" to "10 or less" unless otherwise specified.

<Diphenylethene compound>
A first embodiment of the present invention is a diphenylethene compound represented by general formula (I).

In formula (I), R ₁ to R ₁₀ are each independently,
Hydrogen atom, halogen atom, cyano group, sulfone group,
substituted or unsubstituted alkyl group,
substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group,
substituted or unsubstituted aralkyl group,
substituted or unsubstituted aryl group,
substituted or unsubstituted alkylcarbonyl group,
substituted or unsubstituted arylcarbonyl group,
substituted or unsubstituted carboxylic acid ester group,
substituted or unsubstituted sulfonic acid ester group,
-SR, -OR, or -NRR'.
In the formula, R and R' each independently represent a hydrogen atom,
Substituted or unsubstituted alkyl group having 2 or more carbon atoms,
substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group,
a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group,
represents.
R ₁ to R ₁₀ may be bonded to each other to form an aliphatic ring or an aromatic ring.
However, at least one of R ₁ to R ₁₀ represents -SR.

R ₁₁ and R ₁₂ are each independently,
Halogen atom, cyano group, nitro group, formyl group, carboxy group, sulfone group,
substituted or unsubstituted alkyl group,
substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group,
substituted or unsubstituted aralkyl group,
substituted or unsubstituted aryl group,
substituted or unsubstituted alkylcarbonyl group,
substituted or unsubstituted arylcarbonyl group,
substituted or unsubstituted arylsulfonyl group,
Substituted or unsubstituted carboxylic acid ester group, or substituted or unsubstituted sulfonic acid ester group,
represents.
R ₁₁ and R ₁₂ may be combined with each other to form an aliphatic ring or an aromatic ring.

In R ₁ to R ₁₀ shown in formula (I),
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, and preferably a chlorine atom and a fluorine atom.

Examples of the substituted or unsubstituted alkyl group include those having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms, and more preferably 2 to 8 carbon atoms.
Examples of unsubstituted alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and isopentyl group. , neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, Examples include straight chain or branched unsubstituted alkyl groups such as 1-methylheptyl group and 2-ethylhexyl group.

Examples of substituted alkyl groups include alkyl groups having alkyloxy groups such as methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-hexyloxymethyl group, and (2-ethylbutyloxy)methyl group;
an alkyl group having an alkenyloxy group such as a 2-(4'-pentenyloxy)ethyl group;
an alkyl group having an aralkyloxy group such as a benzyloxymethyl group or a 2-(benzyloxymethoxy)ethyl group;
an alkyl group having an aryloxy group such as a phenyloxymethyl group, a 4-chlorophenyloxymethyl group, or a 4-(2'-phenyloxyethoxy)butyl group;
an alkyl group having an alkylthio group such as n-butylthiomethyl group and 2-n-octylthioethyl group;
Examples include alkyl groups having a halogen atom such as fluoromethyl group, trifluoromethyl group, perfluoroethyl group, 4-fluorocyclohexyl group, dichloromethyl group, 4-chlorocyclohexyl group, and 7-chloroheptyl group.

Examples of the substituted or unsubstituted alkenyl group include those having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms,
Specifically, vinyl group, propenyl group, 1-butenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 2-cyclopentenyl group, 1-vinylhexyl group, Examples include styryl group, styrylmethyl group, and 2-styrylethyl group.

Examples of the substituted or unsubstituted alkynyl group include those having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms,
Specific examples include acetylenyl group, propynyl group, 1-butynyl group, 1-pentynyl group, 2-pentynyl group, 2-methyl-1-pentynyl group, and phenylacetylenyl group.

Examples of the substituted or unsubstituted aralkyl group include those having 7 to 25 carbon atoms, preferably 7 to 20 carbon atoms,
Specifically, benzyl group, α-methylbenzyl group, phenethyl group, α-methylphenethyl group, α,α-dimethylbenzyl group, α,α-dimethylphenethyl group, 4-methylphenethyl group, 4-methylbenzyl group , an aralkyl group having an unsubstituted or alkyl group such as a 4-isopropylbenzyl group;
Aralkyl group having an aryl group or aralkyl group such as 4-benzylbenzyl group, 4-phenethylbenzyl group, 4-phenylbenzyl group;
4-methoxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-vinyloxymethylbenzyl group, 4 - an aralkyl group having a substituted oxy group such as a benzyloxybenzyl group or a 4-phenethyloxybenzyl group;
Aralkyl groups having a hydroxyl group such as 4-hydroxybenzyl group and 4-hydroxy-3-methoxybenzyl group;
Aralkyl groups having a halogen atom such as 4-fluorobenzyl group, 3-chlorobenzyl group, 3,4-dichlorobenzyl group;
Examples include 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, and 2-naphthylmethyl group.

Examples of the substituted or unsubstituted aryl group include those having 6 to 24 carbon atoms, preferably 6 to 19 carbon atoms. In this specification, the aryl group refers to, for example, a carbocyclic group such as a phenyl group or a naphthyl group. Represents an aromatic group, for example, a heterocyclic aromatic group such as a furyl group, a thienyl group, a pyridyl group, or a pyrazyl group.
Examples of unsubstituted aryl groups include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, 2-pyrenyl group. group, 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group, 8-fluoranthenyl group, 2-furyl group, 2-thienyl group, Examples include 3-thienyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyrazyl group, 4-methylpyrazyl group, 5-methylpyrazyl group, and the like.

Examples of substituted aryl groups include 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-(4'-tert- butylcyclohexyl)phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2,4-dimethylphenyl group, 5-ethyl- Aryl group having an alkyl group such as 2-thienyl group, 5-n-pentyl-2-thienyl group, 5-n-decyl-2-thienyl group, 2-methylpyrazyl group, 4-methylpyrazyl group, 5-methylpyrazyl group;
4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2- Alkoxy such as isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group, 2-phenyloxyphenyl group, etc. or an aryl group having an aryloxy group;
4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 2,6-diphenylphenyl group, 4-(2'-naphthyl)phenyl group, 2-phenyl-1-naphthyl group, 1-phenyl- Aryl group having an aryl group such as 2-naphthyl group, 7-phenyl-1-pyrenyl group, 5-phenyl-2-thienyl group, 5-(2'-thienyl)-2-thienyl group;
4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2,4,6-trichlorophenyl group, 2-chloro-5-methylphenyl group, 2 -Chloro-6-methylphenyl group, 2-methyl-3-chlorophenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoropyrazyl group, 4-fluoropyrazyl an aryl group having a halogen atom, such as a 5-fluoropyrazyl group;
2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4-methylthiophenyl group, 4 -ethylthiophenyl group, 4-cyanophenyl group, 3-cyanophenyl group, etc.

Examples of the substituted or unsubstituted alkylcarbonyl group include those having 2 to 13 carbon atoms, preferably 2 to 8 carbon atoms,
Specifically, acetyl group, propionyl group, butyryl group, valeryl group, iso-valeryl group, sec-valeryl group, trimethylacetyl group, hexanoyl group, t-butylacetyl group, heptanoyl group, octanoyl group, 2-ethylhexane group. Noyl group, nonanoyl group, decanoyl group, undecanoyl group, lauroyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, oleyl group, cyclopentanecarbonyl group, cyclohexane carbonyl group, 6-chlorohexanoyl group, 6-bromohexanoyl group, trifluoroacetyl group, pentafluoropropionyl group, perfluorooctanoyl group, 2,2,4,4,5,5,7,7, Examples include 7-nonafluoro-3,6-dioxaheptanoyl group, methoxyacetyl group, 3,6-dioxaheptanoyl group, and cinnamoyl group.

Examples of the substituted or unsubstituted arylcarbonyl group include those having 7 to 25 carbon atoms, preferably 7 to 20 carbon atoms,
Specifically, benzoyl group, 2-methylbenzoyl group, 3-methylbenzoyl group, 4-methylbenzoyl group, 4-ethylbenzoyl group, 4-n-propylbenzoyl group, 4-tert-butylbenzoyl group, 2, 4-dimethylbenzoyl group, 2,4,6-trimethylbenzoyl group, 2,4,5-trimethylbenzoyl group, 4-ethylbenzoyl group, 4-isopropylbenzoyl group, 4-n-butylbenzoyl group, 4-isobutylbenzoyl group group, 4-sec-butylbenzoyl group, 4-tert-butylbenzoyl group, 4-n-pentylbenzoyl group, 4-isopentylbenzoyl group, 4-neopentylbenzoyl group, 4-isohexylbenzoyl group, 4-sec-butylbenzoyl group, Kilohexylbenzoyl group, 4-octylbenzoyl group, 4-cyanobenzoyl group, 4-nitrobenzoyl group, 4-trifluoromethylbenzoyl group, 3-bromobenzoyl group, 2-fluorobenzoyl group, 4-chlorobenzoyl group, 2 , 6-dichlorobenzoyl group, 2,4-dichlorobenzoyl group, naphthylcarbonyl-1-yl group, naphthylcarbonyl-2-yl group, and the like.

Examples of the substituted or unsubstituted carboxylic acid ester group include those having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms. The carboxylic acid ester group can be represented by the formula: R-O-C(=O)-*, where R is a hydrocarbon group and * represents a bond.
Specifically, the substituted or unsubstituted carboxylic acid ester group includes a carboxylic acid methyl ester group, a carboxylic acid ethyl ester group, a carboxylic acid n-propyl ester group, a carboxylic acid isopropyl ester group, a carboxylic acid n-butyl ester group, Carboxylic acid tert-butyl ester group, carboxylic acid n-pentyl ester group, carboxylic acid isopentyl ester group, carboxylic acid cyclohexyl ester group, carboxylic acid n-octyl ester group, carboxylic acid trifluoropropyl ester group, carboxylic acid benzyl ester group , a carboxylic acid phenyl ester group, a carboxylic acid toluyl ester group, and the like.

Examples of the substituted or unsubstituted sulfonic acid ester group include those having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms. The sulfonic acid ester group can be represented by the formula: R-O-S(=O) ₂ -*, where R is a hydrocarbon group and * represents a bond.
Specifically, the substituted or unsubstituted sulfonic acid ester group includes a sulfonic acid methyl ester group, a sulfonic acid ethyl ester group, a sulfonic acid n-propyl ester group, a sulfonic acid isopropyl ester group, a sulfonic acid n-butyl ester group, Sulfonic acid tert-butyl ester group, sulfonic acid n-pentyl ester group, sulfonic acid isopentyl ester group, sulfonic acid cyclohexyl ester group, sulfonic acid n-octyl ester group, sulfonic acid trifluoropropyl ester group, sulfonic acid benzyl ester group , a sulfonic acid phenyl ester group, a sulfonic acid tolyl ester group, and the like.

The sulfur atom-containing group represented by -SR includes a substituted or unsubstituted alkylthio group having 2 or more carbon atoms, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkenylthio group, a substituted or unsubstituted alkenylthio group, Examples include an alkynylthio group and a substituted or unsubstituted aralkylthio group.

Examples of the substituted or unsubstituted alkylthio group include those having 2 to 25 carbon atoms, preferably 2 to 15 carbon atoms.
Examples of unsubstituted alkylthio groups include ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, tert-butylthio group, sec-butylthio group, n-pentylthio group, and isopentylthio group. , n-hexylthio group, 2-methylpentylthio group, 1,1-dimethylbutylthio group, 1,2,2-trimethylpropylthio group, 2-ethylbutylthio group, 1,3-dimethylhexylthio group, cyclohexyl Thio group, methylcyclopentylthio group, n-heptylthio group, n-heptylthio group, n-octylthio group, 3,5,5-trimethylhexylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group , 1-adamantylthio group, and n-pentadecylthio group.

Examples of substituted alkylthio groups include trifluoroethylthio group, perfluorodecanethio group, pentafluoropropylthio group, 4-fluorocyclohexylthio group, dichloromethylthio group, 4-chlorocyclohexylthio group, 7-chloroheptylthio group. an alkylthio group having a halogen atom such as a group;
Methoxymethylthio group, ethoxymethylthio group, n-propyloxymethylthio group, n-butyloxymethylthio group, isobutyloxymethylthio group, tert-butyloxymethylthio group, n-pentyloxymethylthio group, 2-methoxyethylthio group, 2- Ethoxyethylthio group, 2-n-propyloxyethylthio group, 2-isopropyloxyethylthio group, 2-n-butyloxyethylthio group, 2-isobutyloxyethylthio group, 2-tert-butyloxyethylthio group , 2-sec-butyloxyethylthio group, 2-n-pentyloxyethylthio group, 2-isopentyloxyethylthio group, 2-sec-pentyloxyethylthio group, 2-n-hexyloxyethylthio group, 2-(4-ethylcyclohexyloxy)ethylthio group, 2-n-nonyloxyethylthio group, 2-(3,5,5-trimethylhexyloxy)ethylthio group, 2-n-decyloxyethylthio group, 2- n-dodecyloxyethylthio group, 3-methoxypropylthio group, 3-ethoxypropylthio group, 3-(n-propylthio)propylthio group, 2-isopentyloxypropylthio group, 2-methoxybutylthio group, 4- Alkylthio groups having alkoxy groups such as ethoxybutylthio group, 4-(n-propyloxy)butylthio group, 5-methoxypentylthio group, 5-ethoxypentylthio group, 6-n-propyloxyhexylthio group;
Methoxymethoxymethylthio group, ethoxymethoxymethylthio group, propyloxymethoxymethylthio group, butyloxymethoxymethylthio group, ethoxyethoxymethylthio group, propyloxyethoxymethylthio group, methoxymethoxyethylthio group, ethoxymethoxyethylthio group, propyloxymethoxyethylthio group group, butyloxymethoxyethylthio group, propyloxyethoxyethylthio group, butyloxyethoxyethylthio group, propyloxybutyloxyethylthio group, methoxymethoxypropylthio group, ethoxymethoxypropylthio group, butyloxymethoxypropylthio group, An alkylthio group having an alkoxyalkoxy group such as a butyloxymethoxybutylthio group, an ethoxyethoxybutylthio group, a cyclohexyloxyethoxyethylthio group, a [4-(3,5,5-trimethylhexyloxy)butyloxy]ethylthio group;
Alkoxycarbonyl groups such as methoxycarbonylmethylthio group, ethoxycarbonylmethylthio group, n-propyloxycarbonylmethylthio group, methoxycarbonylethylthio group, ethoxycarbonylethylthio group, n-propyloxycarbonylethylthio group, ethoxycarbonylpropylthio group, etc. Acylthio group having;
Methylaminomethylthio group, 2-methylaminoethylthio group, 2-(2-methylaminoethoxy)ethylthio group, 4-methylaminobutylthio group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropylthio group group, 2-ethylaminoethylthio group, 2-(2-ethylaminoethoxy)ethylthio group, 3-ethylaminopropylthio group, 1-ethylaminopropylthio group, 2-isopropylaminoethylthio group, 2-(n - an alkylthio group having an alkylamino group such as a butylamino)ethylthio group, a 3-(n-hexylamino)propylthio group, or a 4-(cyclohexylamino)butylthio group;
Dimethylaminomethylthio group, 2-dimethylaminoethylthio group, 4-dimethylaminobutylthio group, 1-dimethylaminopropan-2-ylthio group, 3-dimethylaminopropylthio group, 2-diethylaminoethylthio group, 3-diethylamino Dialkylthio groups such as propylthio group, 2-diisopropylaminoethylthio group, 2-(di-n-butylamino)ethylthio group, 2-piperidylethylthio group, 3-(di-n-hexylamino)propylthio group, etc. an alkylthio group;
Methylthiomethylthio group, 2-methylthioethylthio group, 2-ethylthioethylthio group, 2-n-propylthioethylthio group, 2-isopropylthioethylthio group, 2-n-butylthioethylthio group, 2-isobutyl an alkylthio group having an alkylthio group such as a thioethylthio group or a (3,5,5-trimethylhexylthio)hexylthio group;
2-N-morpholinylethylthio group, 2-N-pyridylethylthio group, 2-N-pyrrolylethylthio group, 2-(2-furyl)ethylthio group, 2-(1-indolyl)ethylthio group, 2-(3-thienyl)ethylthio group, 3-N-morpholinylpropylthio group, 3-N-pyridylpropylthio group, 3-N-pyrrolylpropylthio group, 3-(1-indolyl)propylthio group, etc. an alkylthio group having a heterocyclic group;
Aryl groups such as phenylmethylthio group, methylphenylmethylthio group, ethylphenylmethylthio group, tert-butylphenylmethylthio group, phenylethylthio group, methylphenylethylthio group, ethylphenylethylthio group, tert-butylphenylethylthio group Examples include an alkylthio group having

Examples of the substituted or unsubstituted arylthio group include those having 6 to 25 carbon atoms, preferably 6 to 18 carbon atoms,
Specifically, phenylthio group, 2-methylphenylthio group, 4-methylphenylthio group, 3-ethylphenylthio group, 4-n-propylphenylthio group, 4-isopropylphenylthio group, 4-n-butyl Phenylthio group, 4-isobutylphenylthio group, 4-tert-butylphenylthio group, 4-n-pentylphenylthio group, 4-n-hexylphenylthio group, 4-cyclohexylphenylthio group, 4-n-octyl group Phenylthio group, 4-n-dodecylphenylthio group, 4-n-octadecylphenylthio group, 2,4-dimethylphenylthio group, 2,5-dimethylphenylthio group, 3,4-dimethylphenylthio group, 2 , 4,6-trimethylphenylthio group, 5-indanylthio group, 1,2,3,4-tetrahydro-6-naphthylthio group, 2-methoxyphenylthio group, 3-methoxyphenylthio group, 4-methoxyphenylthio group , 4-ethoxyphenylthio group, 4-n-propoxyphenylthio group, 2,4-dimethoxyphenylthio group, 3,5-diethoxyphenylthio group, 2-methoxy-4-methylphenylthio group, 2-methyl -4-methoxyphenylthio group, 2-fluorophenylthio group, 4-fluorophenylthio group, 2-chlorophenylthio group, 4-chlorophenylthio group, 4-bromophenylthio group, 4-trifluoromethylphenylthio group, 3-trifluoromethylphenylthio group, 2,4-difluorophenylthio group, 2,4-dichlorophenylthio group, 2,4,6-trifluorophenylthio group, 2,4,6-trichlorophenylthio group, 2 -Chloro-4-methoxyphenylthio group, 2-naphthylthio group, 4-methyl-1-naphthylthio group, 4-ethoxy-1-naphthylthio group, 2-pyridylthio group, 4-aminophenylthio group, 4-(N, N-dimethylamino)phenylthio group, 4-(N,N-diethylamino)-1-naphthylthio group, 4-[N,N-di(4'-methylphenyl)amino]phenylthio group, 4-(N-phenoxadi yl) phenylthio group, 4-hydroxyphenylthio group, 2,4-dihydroxyphenylthio group, 4-methylthiophenylthio group, etc.

Examples of the substituted or unsubstituted alkenylthio group include those having 2 to 25 carbon atoms, preferably 2 to 15 carbon atoms, and examples of the alkenyl group in the alkenylthio group include the same specific examples as the above-mentioned alkenyl group. The same applies to substituents that may be included.

Examples of the substituted or unsubstituted alkynylthio group include those having 2 to 25 carbon atoms, preferably 2 to 15 carbon atoms, and examples of the alkynyl group in the alkynylthio group include, for example, the same specific examples as the alkynyl group described above. The same applies to the substituents that it may have.

Examples of the substituted or unsubstituted aralkylthio group include those having 7 to 25 carbon atoms, preferably 7 to 15 carbon atoms, and examples of the aralkyl group in the aralkylthio group include, for example, the same specific examples as the aralkyl group described above. The same applies to the substituents that it may have.

The oxygen atom-containing group represented by -OR includes a hydroxyl group, a substituted or unsubstituted alkoxy group having 2 or more carbon atoms, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkenyloxy group, a substituted Alternatively, examples thereof include an unsubstituted alkynyloxy group and a substituted or unsubstituted aralkyloxy group.

Examples of the substituted or unsubstituted alkoxy group include those having 2 to 25 carbon atoms, preferably 2 to 15 carbon atoms.
Examples of unsubstituted alkoxy groups include ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, sec-butyloxy group, n-pentyloxy group, Isopentyloxy group, n-hexyloxy group, 2-methylpentyloxy group, 1,1-dimethylbutyloxy group, 1,2,2-trimethylpropyloxy group, 2-ethylbutyloxy group, 1,3-dimethyl Hexyloxy group, cyclohexyloxy group, methylcyclopentyloxy group, n-heptyloxy group, n-heptyloxy group, n-octyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-un Examples include straight chain, branched or cyclic unsubstituted alkoxy groups such as decyloxy group, n-dodecyloxy group, 1-adamantyloxy group, and n-pentadecyloxy group.

Examples of substituted alkoxy groups include methoxymethoxy group, ethoxymethoxy group, n-propyloxymethoxy group, n-butyloxymethoxy group, isobutyloxymethoxy group, tert-butyloxymethoxy group, n-pentyloxymethoxy group. , 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propyloxyethoxy group, 2-isopropyloxyethoxy group, 2-n-butyloxyethoxy group, 2-isobutyloxyethoxy group, 2-tert-butyl Oxyethoxy group, 2-sec-butyloxyethoxy group, 2-n-pentyloxyethoxy group, 2-isopentyloxyethoxy group, 2-tert-pentyloxyethoxy group, 2-sec-pentyloxyethoxy group, 2- Cyclopentyloxyethoxy group, 2-n-hexyloxyethoxy group, 2-(4-ethylcyclohexyloxy)ethoxy group, 2-n-nonyloxyethoxy group, 2-(3,5,5-trimethylhexyloxy)ethoxy group , 2-n-decyloxyethoxy group, 2-n-dodecyloxyethoxy group, 3-methoxypropyloxy group, 3-ethoxypropyloxy group, 3-(n-propyloxy)propyloxy group, 2-isopentyloxy group Propyloxy group, 2-methoxybutyloxy group, 4-ethoxybutyloxy group, 4-(n-propyloxy)butyloxy group, 4-isopropyloxybutyloxy group, 5-methoxypentyloxy group, 5-ethoxymethoxy group, an alkoxy group having an alkoxy group such as 6-n-propylhexyloxy group;
Methoxymethoxymethoxy group, ethoxymethoxymethoxy group, propyloxymethoxymethoxy group, butyloxymethoxymethoxy group, methoxyethoxymethoxy group, ethoxyethoxymethoxy group, propyloxyethoxymethoxy group, methoxymethoxyethoxy group, ethoxymethoxyethoxy group, propyloxy Methoxyethoxy group, butyloxymethoxyethoxy group, propyloxyethoxyethoxy group, butyloxyethoxyethoxy group, propyloxybutyloxyethoxy group, methoxymethoxypropyloxy group, ethoxymethoxypropyloxy group, butyloxymethoxypropyloxy group, methoxymethoxy Butyloxy group, ethoxymethoxybutyloxy group, butyloxymethoxybutyloxy group, ethoxyethoxybutyloxy group, (4-ethylcyclohexyloxy)ethoxyethoxy group, [4-(3,5,5-trimethylhexyloxy)butyloxy] An alkoxy group having an alkoxyalkoxy group such as an ethoxy group;
An alkoxy group having an alkoxycarbonyl group such as a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group, an n-propyloxycarbonylmethoxy group, an isopropyloxycarbonylmethoxy group, and a (4'-ethylcyclohexyloxy)carbonylmethoxy group;
An alkoxy group having an alkoxycarbonyl group such as a methoxycarbonylethoxy group, an ethoxycarbonylethoxy group, an n-propyloxycarbonylethoxy group, an ethoxycarbonylpropyloxy group;
Methylaminomethoxy group, 2-methylaminoethoxy group, 2-(2-methylaminoethoxy)ethoxy group, 4-methylaminobutyloxy group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropyloxy group , 2-methylamino-2-methylpropyloxy group, 2-ethylaminoethoxy group, 2-(2-ethylaminoethoxy)ethoxy group, 3-ethylaminopropyloxy group, 1-ethylaminopropyloxy group, 2- an alkoxy group having an alkylamino group such as an isopropylaminoethoxy group, a 2-(n-butylamino)ethoxy group, a 3-(n-hexylamino)propyloxy group, a 4-(cyclohexylamino)butyloxy group;
Dimethylaminomethoxy group, 2-dimethylaminoethoxy group, 2-(2-dimethylaminoethoxy) ethoxy group, 4-dimethylaminobutyloxy group, 1-dimethylaminopropan-2-yloxy group, 3-dimethylaminopropyloxy group , 2-dimethylamino-2-methylpropyloxy group, 2-diethylaminoethoxy group, 2-(2-diethylaminoethoxy)ethoxy group, 3-diethylaminopropyloxy group, 1-diethylaminopropyloxy group, 2-diisopropylaminoethoxy group , 2-(di-n-butylamino)ethoxy group, 2-piperidylethoxy group, 3-(di-n-hexylamino)propyloxy group, etc., an alkoxy group having a dialkylamino group;
an alkoxy group having an alkylaminoalkoxy group such as a methylaminomethoxymethoxy group, a methylaminoethoxyethoxy group, a methylaminoethoxypropyloxy group, an ethylaminoethoxypropyloxy group, a 4-(2'-isobutylaminopropyloxy)butyloxy group;
an alkoxy group having a dialkylaminoalkoxy group such as a dimethylaminomethoxymethoxy group, a dimethylaminoethoxyethoxy group, a dimethylaminoethoxypropyloxy group, a diethylaminoethoxypropyloxy group, and a 4-(2'-diisobutylaminopropyloxy)butyloxy group;
Methylthiomethoxy group, 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-isopropylthioethoxy group, 2-n-butylthioethoxy group, 2-isobutylthioethoxy group, ( an alkoxy group having an alkylthio group such as 3,5,5-trimethylhexylthio)hexyloxy group;
2-N-morpholinylethoxy group, 2-N-pyridylethoxy group, 2-N-pyrrolylethoxy group, 2-(2-furyl)ethoxy group, 2-(1-indolyl)ethoxy group, 2-( 3-thienyl)ethoxy group, 3-N-morpholinylpropyloxy group, 3-N-pyridylpropyloxy group, 3-N-pyrrolylpropyloxy group, 3-(1-indolyl)propyloxy group, etc. Examples include alkoxy groups having a ring group.

Examples of the substituted or unsubstituted aryloxy group include those having 6 to 25 carbon atoms, preferably 6 to 18 carbon atoms,
Specifically, phenyloxy group, 2-methylphenyloxy group, 4-methylphenyloxy group, 4-ethylphenyloxy group, 4-isopropylphenyloxy group, 4-isobutylphenyloxy group, 4-n-pentylphenyl Oxy group, 4-tert-pentylphenyloxy group, 4-cyclohexylphenyloxy group, 4-n-octylphenyloxy group, 4-n-decylphenyloxy group, 4-n-dodecylphenyloxy group, 4-n- Hexadecyl phenyloxy group, 2,3-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,4,5-trimethylphenyloxy group, 5-indanyloxy group , 1,2,3,4-tetrahydro-6-naphthyloxy group, 3-methoxyphenyloxy group, 3-ethoxyphenyloxy group, 4-n-propoxyphenyloxy group, 4-n-butoxyphenyloxy group, 4 -n-pentyloxyphenyloxy group, 4-cyclohexyloxyphenyloxy group, 4-n-octyloxyphenyloxy group, 4-n-decyloxyphenyloxy group, 4-n-dodecyloxyphenyloxy group, 4-n -hexadecyloxyphenyloxy group, 2,3-dimethoxyphenyloxy group, 2,5-dimethoxyphenyloxy group, 3,5-dimethoxyphenyloxy group, 2-methoxy-4-methylphenyloxy group, 3-methoxy- 4-methylphenyloxy group, 3-methyl-4-methoxyphenyloxy group, 2-fluorophenyloxy group, 4-fluorophenyloxy group, 3-chlorophenyloxy group, 4-bromophenyloxy group, 3-trifluoromethyl Phenyloxy group, 3,5-difluorophenyloxy group, 3,4-dichlorophenyloxy group, 2-methyl-4-chlorophenyloxy group, 3-chloro-4-methylphenyloxy group, 3-methoxy-4-fluorophenyl group Oxy group, 3-fluoro-4-methoxyphenyloxy group, 4-phenylphenyloxy group, 3-phenylphenyloxy group, 4-(4'-methylphenyl)phenyloxy group, 4-(4'-methoxyphenyl) Phenyloxy group, 1-naphthyloxy group, 4-methyl-1-naphthyloxy group, 6-n-butyl-2-naphthyloxy group, 7-ethoxy-2-naphthyloxy group, 2-thienyloxy group, 2- Pyridyloxy group, 4-pyridyloxy group, 2-furyloxy group, 5-ethyl-2-thienyloxy group, 5-n-pentyl-2-thienyloxy group, 5-n-decyl-2-thienyloxy group, Examples include 5-phenyl-2-thienyloxy group, 5-(2'-thienyl)-2-thienyloxy group, 3-thienyloxy group, and 3-pyridyloxy group.

Examples of the substituted or unsubstituted alkenyloxy group include those having 2 to 25 carbon atoms, preferably 2 to 15 carbon atoms, and examples of the alkenyl group in the alkenyloxy group include the same specific examples as the above-mentioned alkenyl group. The same applies to substituents that may be included.

Examples of the substituted or unsubstituted alkynyloxy group include those having 2 to 25 carbon atoms, preferably 2 to 15 carbon atoms, and examples of the alkynyl group in the alkynyloxy group include, for example, the same specific examples as the alkynyl group described above. The same applies to the substituents that it may have.

Examples of the substituted or unsubstituted aralkyloxy group include those having 7 to 25 carbon atoms, preferably 7 to 20 carbon atoms, and examples of the aralkyl group in the aralkyloxy group include, for example, the same specific examples as the aralkyl group described above. The same applies to the substituents that it may have.

Examples of the nitrogen atom-containing group represented by -NRR' include an amino group and an amino group having a substituent, and examples of the substituent include the above-mentioned alkyl group having 2 or more carbon atoms, an aryl group, Specific examples similar to those of the aralkyl group, alkenyl group, and alkynyl group are mentioned, and the substituents that may be included are also the same. in particular,
Ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, cyclohexylamino group, 3,5,5-trimethylhexylamino group, nonylamino group group, monoalkylamino group such as decylamino group;
Dialkyl amino groups such as diethylamino group, di-n-propylamino group, di-n-butylamino group, di-n-pentylamino group, N-ethyl-N-isopropylamino group, N-ethyl-N-cyclohexylamino group, etc. Base;
N-ethyl-N-phenylamino group, N-ethyl-N-(2,4-dimethylphenyl)amino group, Nn-propyl-N-(2-ethoxyphenyl)amino group, diphenylamino group, di- An amino group having an aryl group such as a (p-tolyl) amino group or an N-methyl-N-(2-naphthyl) amino group;
Benzylamino group, phenethylamino group, 3-phenylpropylamino group, 4-ethylbenzylamino group, 4-isopropylbenzylamino group, dibenzylamino group, diphenethylamino group, bis(4-ethylbenzyl)amino group, bis Examples include amino groups having an aralkyl group such as (4-isopropylbenzyl)amino group and N-ethyl-N-benzylamino group.

In formula (I), the groups R ₁ to R ₁₀ are
Hydrogen atoms, hydroxyl groups,
a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms,
a substituted or unsubstituted aralkyl group having 7 to 25 carbon atoms,
a substituted or unsubstituted aryl group having 6 to 24 carbon atoms,
a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms; a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms;
A substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms,
At least one of R ₁ to R ₁₀ is a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms, a substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms, or a substituted or unsubstituted aralkylthio group having 6 to 25 carbon atoms. 18 arylthio groups,
The groups R ₁ to R ₁₀ are
hydroxyl group,
a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms,
a substituted or unsubstituted aryl group having 6 to 24 carbon atoms,
a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms,
A substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms,
At least one of R ₁ to R ₁₀ is a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms, a substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms, or a substituted or unsubstituted aralkylthio group having 6 to 25 carbon atoms. The case of arylthio group of 18 is preferable,
The groups R ₁ , R ₃ and R ₈ are
hydroxyl group,
a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms,
a substituted or unsubstituted aryl group having 6 to 24 carbon atoms,
a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms,
A substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms,
At least one of R ₁ , R ₃ and R ₈ is a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms, a substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms, or a substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms. More preferably, the number is 6 to 18 arylthio groups,
At least one of R ₃ and R ₈ is
a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms,
a substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms,
More preferred is a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms.

R ₁ to R ₁₀ may be linked to each other to form a ring. When forming a ring, usually adjacent R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ , R ₆ and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ and R ₉ and R ₁₀ are connected to form a ring containing the carbon atom to which each bond is attached. The ring thus formed is preferably a substituted or unsubstituted carbocyclic aliphatic ring, a substituted or unsubstituted carbocyclic aromatic ring, a substituted or unsubstituted heterocyclic aliphatic ring, or Mention may be made of substituted or unsubstituted heteroaromatic rings,
More preferably,
a substituted or unsubstituted carbocyclic aliphatic ring having a total of 5 to 20 carbon atoms,
a substituted or unsubstituted carbocyclic aromatic ring having a total of 6 to 20 carbon atoms,
a substituted or unsubstituted heterocyclic aliphatic ring having a total of 4 to 20 carbon atoms,
Alternatively, a substituted or unsubstituted heteroaromatic ring having a total of 4 to 20 carbon atoms can be mentioned, in which at least one of adjacent R ₁ and R ₂ or R ₉ and R ₁₀ are connected.

Specific examples of carbocyclic aliphatic rings include:
Examples include a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cyclooctane ring, and a cyclodesane ring.
Specific examples of carbocyclic aromatic rings include:
For example, a benzene ring, a naphthalene ring, etc. can be mentioned.
Specific examples of heterocyclic aliphatic rings include:
Examples include a dihydrofuran ring, a dihydrothiophene ring, a dioxane ring, and a dithian ring.
Specific examples of heterocyclic aromatic rings include:
Examples include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a pyrrole ring, and a silole ring.
Note that the formed carbocyclic aliphatic ring, carbocyclic aromatic ring, heterocyclic aliphatic ring, and heterocyclic aromatic ring may have a substituent.
Examples of the substituent include a halogen atom, a carboxyl group, a cyano group, a nitro group, a hydroxyl group, a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, a straight chain, branched or cyclic group having 1 to 20 carbon atoms, Cyclic alkoxy group, halogen atom, carboxyl group, cyano group, nitro group, hydroxyl group, straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, straight chain, branched or cyclic having 1 to 20 carbon atoms may be substituted with an aryl group which may be substituted with an alkoxy group, or may be substituted with a plurality of aryl groups.

Then, in R ₁₁ and R ₁₂ shown in formula (I),
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, and preferably a chlorine atom and a fluorine atom.

Substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkylcarbonyl group, substituted Or unsubstituted arylcarbonyl group, substituted or unsubstituted carboxylic acid ester group, substituted or unsubstituted sulfonic acid ester group,
For example, the specific examples mentioned above for R ₁ to R ₁₀ may be mentioned, and preferred specific examples are also the same.

Examples of the substituted or unsubstituted arylsulfonyl group include those having 6 to 24 carbon atoms, preferably 6 to 18 carbon atoms,
Specifically, phenylsulfonyl group, 2-methylphenylsulfonyl group, 3-methylphenylsulfonyl group, 4-methylphenylsulfonyl group, 4-ethylphenylsulfonyl group, 4-n-propylphenylsulfonyl group, 4-tert- Butylphenylsulfonyl group, 2,4-dimethylphenylsulfonyl group, 2,4,6-trimethylphenylsulfonyl group, 2,4,5-trimethylphenylsulfonyl group, 4-ethylphenylsulfonyl group, 4-isopropylphenylsulfonyl group, 4-n-butylphenylsulfonyl group, 4-isobutylphenylsulfonyl group, 4-sec-butylphenylsulfonyl group, 4-tert-butylphenylsulfonyl group, 4-n-pentylphenylsulfonyl group, 4-isopentylphenylsulfonyl group , 4-neopentylphenylsulfonyl group, 4-isohexylphenylsulfonyl group, 4-cyclohexylphenylsulfonyl group, 4-octylphenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-nitrophenylsulfonyl group, 4-tri Examples include fluoromethylphenylsulfonyl group, 3-bromophenylsulfonyl group, 2-fluorophenylsulfonyl group, 4-chlorophenylsulfonyl group, 2,6-dichlorophenylsulfonyl group, 2,4-difluorophenylsulfonyl group, naphthylsulfonyl group, etc. It will be done.

In formula (I), as the groups R ₁₁ and R ₁₂ ,
Halogen atom, cyano group, nitro group, formyl group, carboxy group, sulfone group,
unsubstituted alkyl group,
substituted or unsubstituted aryl group,
substituted or unsubstituted halogenated alkyl group,
substituted or unsubstituted alkylcarbonyl group,
substituted or unsubstituted arylcarbonyl group,
substituted or unsubstituted arylsulfonyl group,
A substituted or unsubstituted carboxylic acid ester group or a substituted or unsubstituted sulfonic acid ester group is preferred,
At least one of R ₁₁ and R ₁₂ is a cyano group, a nitro group, a formyl group, a carboxy group, a sulfone group,
unsubstituted alkyl group having 1 to 20 carbon atoms; substituted or unsubstituted halogenated alkyl group having 1 to 20 carbon atoms;
a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
a substituted or unsubstituted arylsulfonyl group having 6 to 24 carbon atoms,
More preferred is a substituted or unsubstituted carboxylic acid ester group having 2 to 20 carbon atoms or a substituted or unsubstituted sulfonic acid ester group having 2 to 20 carbon atoms.
At least one of R ₁₁ and R ₁₂ is a cyano group, a nitro group,
Substituted or unsubstituted halogenated alkyl group having 1 to 20 carbon atoms,
Substituted or unsubstituted carboxylic acid ester group having 2 to 20 carbon atoms,
Particularly preferred is a substituted or unsubstituted sulfonic acid ester group having 2 to 20 carbon atoms.

Examples of substituted or unsubstituted halogenated alkyl groups include those having 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms, and more preferably 2 to 15 carbon atoms. Examples of substituted alkyl groups with R ₁ to R ₁₀ include Examples include the alkyl group having a halogen atom described above, and preferred specific examples are also the same.

In formula (I), R ₁₁ and R ₁₂ may be linked to each other to form a ring, including a substituted or unsubstituted carbocyclic aromatic ring, a substituted or unsubstituted carbocyclic aliphatic ring, a substituted or An unsubstituted nitrogen-containing heterocyclic aliphatic ring, or a substituted or unsubstituted oxygen-containing heterocyclic aliphatic ring is preferred; a substituted or unsubstituted carbocyclic aliphatic ring, or a substituted or unsubstituted nitrogen-containing heterocyclic aliphatic ring Cycloaliphatic rings are more preferred.

Specifically, for example, barbituric ring, dimethylbarbituric ring, diethylbarbituric ring, dicyclohexylbarbituric ring, diphenylbarbituric ring, thiobarbituric ring, dimethylthiobarbituric ring, diethylthiobarbituric ring, dicyclohexylthio Examples thereof include a barbituric ring, a diphenylthiobarbituric ring, an indanedione ring, a benzoindanedione ring, and a Meldrum ring.

In this embodiment, the ring structure formed by connecting R ₁₁ and R ₁₂ to each other is preferably a ring structure represented by the following formula (i) or the following formula (ii).

In formula (i), n is 0 or 1, and * represents a bond.
In formula (ii), Q ₁ to Q ₃ each independently represent an oxygen atom or a sulfur atom, and it is preferred that at least two of them are oxygen atoms.
X ₁ and X ₂ each independently represent an alkyl group, an alicyclic group, or an aromatic group having 1 to 3 carbon atoms. * indicates a bond.
Examples of the alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the aromatic group include a phenyl group, a naphthalene group, and a biphenyl group.

As the diphenylethene compound represented by the formula (I) of the present embodiment, from the viewpoint of the effects of the present invention, a diphenylethene compound represented by the following formula (Ia) can be preferably mentioned.

In formula (Ia), Ra is a group other than -SR of R ₁ to R ₁₀ of formula (I), and two Ras may be the same or different.
m1 and m2 are each independently an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1. Both m1 and m2 never become 0. n1 and n2 are each an integer of 0 to 5, preferably an integer of 3 to 5, more preferably 4 or 5. However, the total of m1 and n1 is 5, and the total of m2 and n2 is 5.
R is the same as R in -SR in formula (I).
R ₁₁ is the same as R ₁₁ in formula (I), and R ₁₂ is the same as R ₁₂ in formula (I).

The diphenylethene compound represented by formula (I) of this embodiment is not limited as long as it can reduce the transmittance in the ultraviolet region, but it is adjusted to a toluene solution with a concentration of 0.01 g/L, and the spectral light intensity is When the maximum absorption wavelength is measured in the wavelength range of 300nm to 800nm with an optical path length of 10mm using a meter (for example, Shimadzu spectrophotometer UV-3600iplus manufactured by Shimadzu Corporation), the maximum absorption wavelength is 300nm to 450nm. The wavelength is preferably 330 nm to 400 nm, and even more preferably 350 nm to 380 nm.
Thereby, when shielding light using the diphenylethene compound of this embodiment, the transmittance of blue light can be reduced more favorably.

Specific examples of the diphenylethene compound represented by formula (I) are shown below, but the diphenylethene compound of this embodiment is not limited to these ranges.

<Production method of diphenylethene compound>
The diphenylethene compound represented by formula (I) may be produced by a known method. For example, it can be produced by the method described in WO2015-068839A1, JP-A-2021-24840, and the like.

In this embodiment, a method for producing a diphenylethene compound of formula (Ia) will be described as an example.
The method is, for example, as shown in the reaction formula below,
A step a of reacting a halobenzophenone derivative of the following formula (a) with a sulfur atom-containing derivative of the following formula (b) to obtain a sulfide compound represented by the following formula (c);
Next, step b of reacting the sulfide body of the following formula (c) with the compound of the following formula (d) by Knoevenagel condensation;
including.

In step a, the halobenzophenone derivative (a) of the above formula (a) is reacted with the sulfur atom-containing derivative (b) of the above formula (b) in the presence of potassium carbonate in N,N-dimethylformamide. let

In formula (a), Ra is a group other than -SR in R ₁ to R ₁₀ of formula (I), and two Ras may be the same or different. X represents a halogen atom.
m1 and m2 are each independently an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1. Both m1 and m2 never become 0. n1 and n2 are each an integer of 0 to 5, preferably an integer of 3 to 5, more preferably 4 or 5. However, the total of m1 and n1 is 5, and the total of m2 and n2 is 5.
In formula (b), R is the same as R in -SR of formula (I).

The reaction in step a can be carried out in the atmosphere, the reaction temperature is 80° C. to 150° C., and the reaction time is about 1 hour to 8 hours.
The functional group molar ratio (b/a) of the thiol group of the derivative (b) to X (halogen atom) of the derivative (a) can be 1.0 to 1.2.
Examples of organic solvents other than N,N-dimethylformamide include N,N-dimethylacetamide, 1,2-dimethoxyethane, and 1,2-diethoxyethane.

Through step a, a sulfide compound (c) represented by formula (c) can be obtained. Specifically, it is obtained as a reaction solution containing the sulfide compound (c), and can be used in step b without purification.
Ra, R, m1 and m2, n1 and n2 in formula (c) are the same as Ra, R, m1 and m2, n1 and n2 in formula (a) and formula (b).

In step b, the sulfide compound (c) of the above formula (c) and the compound (d) of the above formula (d) are reacted by Knoevenagel condensation. Thereby, the diphenylethene compound of the above formula (Ia) can be synthesized.
The reaction in step b can be carried out in the atmosphere, the reaction temperature is 20°C to 80°C, and the reaction time is about 30 minutes to 2 hours.
The amount of compound (d) added can be set at a molar ratio (d/c) to sulfide (c) of 1.0 to 1.2.
The reaction in step b can be carried out in the presence of a catalyst, and examples of the catalyst include piperidine, 4-methylmorpholine, 4-ethylmorpholine, titanium tetrachloride, and the like.
After the reaction in step b, a diphenylethene compound of formula (Ia) can be obtained by performing known purification if necessary.

In addition, Ra, R, m1 and m2, n1 and n2 in formula (Ia) are the same as Ra, R, m1 and m2, n1 and n2 in formula (a) and formula (b), and the formula ( d) and R ₁₁ and R ₁₂ in formula (Ia) are the same as R ₁₁ and R ₁₂ in formula (I).

<Light absorber>
Next, a light absorbent according to a second embodiment of the present invention will be described.
The light absorbent of this embodiment contains the above-mentioned diphenylethene compound. By containing the above-mentioned diphenylethene compound, the light absorbent of this embodiment has excellent absorption of light in the vicinity of 400 nm, and as a result, it can satisfactorily reduce the transmittance of blue light and absorb light for a long time. Decrease in light absorption efficiency due to irradiation can be suppressed.

The light absorbent may be in the form of powder, ink, or solution, and the above-mentioned diphenylethene compounds contained in the light absorbent may be one type or a combination of two or more types.

The amount of the diphenylethene compound contained in the light absorber is not particularly limited as long as it can impart desired light absorption properties to the light absorber. The content of the diphenylethene compound can be 100 parts by mass based on 100 parts by mass of the light absorber. That is, the light absorbent of this embodiment can be the same as the above-mentioned diphenylethene compound. Of course, the content of the above-mentioned diphenylethene compound is less than 100 parts by mass with respect to 100 parts by mass of the light absorber, that is, the light absorber is a composition containing the above-mentioned diphenylethene compound and other components. In this case, the amount of the above-mentioned diphenylethene compound is preferably 50 parts by mass or more and 95 parts by mass or less.
Note that the other components are the same as "other additives" described in the "resin composition" section, and will therefore be omitted.

<Resin composition>
Next, a resin composition according to a third embodiment of the present invention will be described.
The resin composition of this embodiment includes the above-mentioned diphenylethene compound and a resin. Since it contains the above-mentioned diphenylethene compound, it can absorb light (ultraviolet rays, blue light, etc.) and can efficiently absorb light in the blue to violet region.
Furthermore, since the diphenylethene compound of this embodiment efficiently absorbs light in the blue to violet region, even if the amount of diphenylethene compound contained in the resin composition etc. of this embodiment is relatively small, Excellent in this effect.
The content of the diphenylethene compound contained in the resin composition (100 parts by mass) of the present embodiment is preferably 0.01 parts by mass or more and 33 parts by mass or less, more preferably 0.01 parts by mass or more and 20 parts by mass or less. It can be done.

Further, while conventional diphenylethene-based compounds with absorption maximum wavelengths in the range of 300 nm to 450 nm tend to be easily decomposed by light irradiation, the diphenylethene-based compounds of the present embodiment exhibit high light resistance. By using it as a light absorber, the absorption efficiency of light in the blue to violet range of resin compositions and molded objects can be maintained for a long period of time.

Since the resin composition of the present embodiment contains a resin together with the above-mentioned diphenylethene-based compound, it is possible to stably retain the above-mentioned diphenylethene-based compound, and as a result, the above-mentioned diphenylethene-based compound can be used as described below. It can be made into a "molded object".
The content of the resin contained in the resin composition (100 parts by mass) of the present embodiment is preferably 0.01 parts by mass or more and 33 parts by mass or less, more preferably 0.01 parts by mass or more and 20 parts by mass or less. Can be done.
Note that such resins include, for example, thermoplastic resins and thermosetting resins.

(resin)
The thermoplastic resin or thermosetting resin used in the resin composition of this embodiment is preferably a transparent resin.

Examples of the thermoplastic resin include polycarbonate resin, polyamide resin, polyester resin, acrylic resin, polystyrene resin, acrylonitrile-styrene resin, norbornene resin, and cellulose resin.

Among the above, from the viewpoint of the strength of the molded product obtained by molding the resin composition, it is preferable that the thermoplastic resin is at least one selected from polycarbonate resin, polyamide resin, acrylic resin, and polyester resin.

The thermosetting resin is preferably at least one selected from polyurethane resins, polythiourethane resins, and allyl diglycol carbonate resins, from the viewpoint of the refractive index of the molded product obtained by molding the resin composition. .

In the resin composition of the present embodiment, from the viewpoint of the strength or refractive index of a molded product obtained by molding the resin composition, the thermoplastic resin is at least one selected from polycarbonate resin, polyamide resin, acrylic resin, and polyester resin. It is preferable that the thermosetting resin is at least one selected from polyurethane resin, polythiourethane resin, and allyl diglycol carbonate resin. Further, from the same viewpoint as above, in the resin composition of the present embodiment, a polycarbonate resin as the thermoplastic resin or a polythiourethane resin as the thermosetting resin is more preferable.

Polycarbonate resin is a polymer obtained mainly by the phosgene method in which dihydroxydiaryl compounds and phosgene are reacted, or the transesterification method in which dihydroxydiaryl compounds are reacted with carbonate esters such as diphenyl carbonate.

Polycarbonate resins include polycarbonate resins made from 2,2-bis(4-hydroxyphenyl)propane (also called bisphenol A), polycarbonate resins made from 1,1-bis(4-hydroxyphenyl)cyclohexane, 1 , 1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, polycarbonate resin made from 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis It may be a polycarbonate resin produced from [4-(2-hydroxyethyloxy)phenyl]fluorene, a copolymerized polycarbonate resin produced from a mixture of the above dihydroxy compounds, or a mixture of the above polycarbonate resins.

In addition to bisphenol A, dihydroxydiaryl compounds include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2, 2-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4- Hydroxy-3-tert-butylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2 -(hydroxyaryl)alkanes such as bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 1,1-bis(4-dichlorophenyl)propane, (hydroxyaryl)cycloalkanes such as -hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'- Dihydroxydiaryl ethers such as dimethyl diphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide and dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.
These may be used alone or in combination of two or more.
Dihydroxydiaryl compounds may be used in combination with piperazine, dipiperidylhydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, and the like.

Note that the viscosity average molecular weight of the polycarbonate resin is usually 10,000 to 100,000, preferably 10,000 to 400,000.

The dihydroxydiaryl compounds may be used in combination with trivalent or higher phenol compounds as shown below. Examples of trivalent or higher phenols include phloroglucin, 1,3,5-tri-(4-hydroxyphenyl)-benzole, 1,1,1-tri-(4-hydroxyphenyl)-ethane, and the like.

A polyamide resin is a resin having a structure of a dehydrated polycondensate of a diamine compound containing an aromatic or aliphatic group and a dicarboxylic acid compound containing an aromatic or aliphatic group. Here, the aliphatic group also includes an alicyclic aliphatic group. The resin having the structure of a dehydrated polycondensate of diamine compounds and dicarboxylic acid compounds is not necessarily limited to that obtained from a dehydrated polycondensation reaction, for example, ring-opening of one or more lactam compounds. It can also be obtained by polymerization.

The above diamine compounds include hexamethylene diamine, m-xylylene diamine, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, trimethylhexamethylenediamine, bis(aminomethyl)norbornane. , bis(aminomethyl)tetrahydrodicyclopentadiene, etc., and one or more types of these diamine compounds can be selected and used.

Examples of the dicarboxylic acid compounds mentioned above include adipic acid, dodecanedicarboxylic acid, isophthalic acid, terephthalic acid, bis(hydroxycarbonylmethyl)norbornane, bis(hydroxycarbonylmethyl)tetrahydrodicyclopentadiene, etc. One type or two or more types can be selected and used from the following.

Amorphous polyamide resins are particularly preferred from the viewpoint of transparency, and are generally referred to as transparent nylons, such as Grilamid TR-55, Grilamid TR-90, Grilamid TR-XE3805 from MMS, or Trogamid CX from Huls. -7323, etc. can be exemplified.

The acrylic resin is a polymer mainly composed of alkyl methacrylate, and may be a homopolymer of alkyl methacrylate or a copolymer using two or more types of alkyl methacrylate, or a polymer containing 50% by mass of alkyl methacrylate. % or more and 50% by mass or less of a monomer other than alkyl methacrylate. As the alkyl methacrylate, those having an alkyl group of 1 to 4 carbon atoms are usually used, and among them, methyl methacrylate is preferably used.

Furthermore, the monomer other than the alkyl methacrylate may be a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule, or a monomer having two or more polymerizable carbon atoms in the molecule. -Although polyfunctional monomers having a carbon double bond may be used, monofunctional monomers are particularly preferably used. Examples include alkyl acrylates such as methyl acrylate and ethyl acrylate, styrenic monomers such as styrene and alkylstyrene, and unsaturated nitriles such as acrylonitrile and methacrylonitrile.

The acrylic resin is a polymer in which the monomer consists essentially only of alkyl methacrylates, or alkyl methacrylates account for, for example, 70% by mass or more, preferably 90% by mass or more of the monomer composition, and The copolymer is preferably a copolymer with substantially only a monomer selected from alkyl acrylates, styrenic monomers, and unsaturated nitriles. In particular, a polymer in which the monomer consists essentially only of alkyl methacrylate is most preferred, and a typical example thereof is polymethyl methacrylate resin (PMMA). Many commercially available polymethyl methacrylate resins are available, such as MX150 manufactured by Soken Chemical, Epostor MA manufactured by Nippon Shokubai, and MBX series manufactured by Sekisui Plastics.

Furthermore, among acrylic resins, poly(meth)acrylic acid ester resins having a low glass transition temperature, for example, a glass transition temperature of less than 0°C, preferably -20°C or less, are used as pressure-sensitive adhesives, adhesives, etc. It is widely used for bonding layers of optical filters for thin displays, or for adhering optical filters and display screens.

The resin composition of this embodiment may be a resin composition containing a quinophthalone compound and a tetraazaporphyrin compound as the organic dye in the adhesive of the poly(meth)acrylate resin. .

The poly(meth)acrylic ester resin used as the adhesive is preferably one containing 50% by mass or more of a (meth)acrylic ester having an alkyl group having 1 to 14 carbon atoms as a monomer.

Examples of (meth)acrylic esters having an alkyl group having 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n -octyl (meth)acrylate, i-octyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and the like.

Other examples of copolymerizable monomers include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, etc. (meth)acrylates; styrenic monomers represented by α-methylstyrene, vinyltoluene, styrene, etc.; vinyl ether monomers represented by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc.; fumaric acid, Monoalkyl esters of acids, dialkyl esters of fumaric acid; maleic acid, monoalkyl esters of maleic acid, dialkyl esters of maleic acid, itaconic acid, monoalkyl esters of itaconic acid, dialkyl esters of itaconic acid, (meth)acrylonitrile, chloride Examples include vinyl, vinylidene chloride, vinyl acetate, vinyl ketone, vinylpyridine, and vinylcarbazole.

Typical polyester resins include homopolyesters such as polyC2-4 alkylene terephthalate and polyC2-4 alkylene naphthalate, and C2-4 alkylene arylate units (C2-4 alkylene terephthalate and/or C2-4 alkylene naphthalate units). ) as a main component, but also include polyarylate resins, aliphatic polyesters using aliphatic dicarboxylic acids such as adipic acid, and single or copolymers of lactones such as ε-caprolactone.

As a copolyester, a part of C2-4 alkylene glycol among the structural units of polyC2-4 alkylene arylate can be replaced with polyoxyC2-4 alkylene glycol, C6-10 alkylene glycol, alicyclic diol (cyclohexanedimethanol, water substituted with diols having aromatic rings (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene with fluorenone side chain, bisphenol A, bisphenol A-alkylene oxide adducts, etc.), etc.) These include copolyesters in which a portion of an aromatic dicarboxylic acid is substituted with an asymmetric aromatic dicarboxylic acid such as phthalic acid or isophthalic acid, or an aliphatic C6-12 dicarboxylic acid such as adipic acid.

As the polyester resin, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. are preferable because of their high transparency. In addition, non-crystalline copolyesters such as C2-4 alkylene arylate copolyesters are also preferable because of their excellent processability. In particular, PET is preferred because it can be produced in large quantities and has excellent heat resistance, strength, and the like.

The polyurethane resin is mainly composed of block polyisocyanate and polyol, and the block polyisocyanate includes hexamethylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, Examples include adducts in which several molecules of each of isophorone diisocyanate and hydrogenated xylylene diisocyanate are bonded together, and those in which isocyanurate or allophanate are blocked with acetoacetic acid or malonic acid. Polyols include polyesters having hydroxyl groups, polyesters, etc. Examples include ether, polycarbonate, polyacrylate, polycaptolactone, and the like.

The polythiourethane resin includes structural units derived from a polyisocyanate compound and structural units derived from a polythiol compound. Moreover, the polythiourethane resin may contain a structural unit derived from a polyol compound in addition to the structural unit derived from a polyisocyanate compound and the structural unit derived from a polythiol compound.
Examples of the polymerizable compound for obtaining the polythiourethane resin include polyisocyanate compounds, polythiol compounds, and polyol compounds.

Examples of the polyisocyanate compound include aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, heterocyclic isocyanate compounds, and araliphatic isocyanate compounds, which may be used singly or in combination of two or more. These isocyanate compounds may include dimers, trimers, and prepolymers. Examples of these isocyanate compounds include compounds exemplified in WO2011/055540.

In this embodiment, from the viewpoint of the effects of the present disclosure, the polyisocyanate compound is 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl ) Bicyclo-[2.2.1]-heptane, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane , 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, and 1,5-pentamethylene diisocyanate,
2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, m-xylylene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane.
The polythiol compound is a compound having two or more mercapto groups, and examples thereof include compounds exemplified in WO2016/125736.

In this embodiment, the polythiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane , 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, penta Erythritol tetrakis (3-mercaptopropionate), bis(mercaptoethyl) sulfide, pentaerythritol tetrakis (2-mercaptoacetate), 2,5-bis(mercaptomethyl)-1,4-dithiane, 1,1,3, selected from 3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane Preferably at least one type of
4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1 , 11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis (3-mercaptopropionate) , and pentaerythritol tetrakis (2-mercaptoacetate).

The polyol compound is one or more aliphatic or alicyclic alcohols, specifically, linear or branched aliphatic alcohols, alicyclic alcohols, and combinations of these alcohols with ethylene oxide, propylene oxide, ε Examples include alcohols to which -caprolactone is added, and specifically, compounds exemplified in WO2016/125736 can be used.

The polyol compound preferably includes ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, At least one type selected from 1,3-cyclohexanediol and 1,4-cyclohexanediol.

As the allyl diglycol carbonate resin, polydiethylene glycol bisallyl carbonate is preferable, and an example thereof includes CR-39 resin (also referred to as ADC resin).

(Other additives)
In addition to the resin and the above-mentioned diphenylethene compound, the resin composition of the present embodiment may contain known ultraviolet absorbers, infrared absorbers, and various resin additives, if necessary.

Various resin additives include phenolic antioxidants, mold release agents, dyes and pigments, phosphorus heat stabilizers, weather resistance improvers, antistatic agents, antifogging agents, lubricants, antiblocking agents, flame retardants, and flowability agents. Examples include improving agents, plasticizers, dispersants, and antibacterial agents.

(Method for manufacturing resin composition)
The method for producing the resin composition of the present embodiment is not particularly limited, and for example, after mixing a thermoplastic resin or thermosetting resin and the above-mentioned diphenylethene compound in a desired ratio in a tumbler, , melt and knead using a single-screw extruder or the like to produce pellets.
Further, the resin composition can be molded into a desired shape using an injection molding machine or the like using the prepared pellets as a raw material.

The molding method varies depending on the type of resin, but in the case of resin compositions using thermoplastic resins, for example, compression molding, transfer molding, extrusion molding, injection molding, etc. are used, and thermosetting resins are used. In the case of the resin composition used, for example, a cast polymerization method or the like may be used.
In addition, in this embodiment, the resin composition after molding may be referred to as a molded article.
The molded body will be explained below.

(molded object)
A molded article, which is one aspect of the resin composition of this embodiment, will be described.
The form of the molded object may be an optical article made of a cured product of the resin composition, an optical article partially containing the cured product of the resin composition, or an optical article such as a powder, pellet, film, etc. It may also be an intermediate material in the manufacture of articles.

Examples of optical articles include eyeglass lenses, sun visors, shields for helmets, anti-glare coats or anti-glare films for display devices of information equipment, filters, covers for lighting equipment, and other anti-glare optical articles. Examples of the above-mentioned filter include optical filters intended to extend the life of image display devices such as liquid crystal display devices and organic EL displays, and to improve contrast in bright rooms.

In the present embodiment, an optical article that partially contains a resin composition refers to an optical article that is contained inside various members or films of the optical article, coated on the surface of the member or each layer, or attached. This includes the state in which

Next, an anti-glare optical article will be described as an example of a molded article.
Anti-glare optical products include eyeglass lenses, sun visors, helmet shields, automobile and airplane windshield films, automobile headlight covers, ski goggles, and anti-glare coats or anti-glare films for information equipment display devices. , filters for LED lighting, etc.

Depending on the functions required for anti-glare optical articles, one or more of anti-reflection function, hard coat function (friction resistance function), antistatic function, antifouling function, gas barrier function, and ultraviolet cut function may be applied. It does not matter if a function is provided.

Next, an optical filter will be described as an example of a molded article.
The optical filter of this embodiment contains the above-mentioned diphenylethene compound in the base material. In the present embodiment, "containing in the base material" means being contained inside the base material, applied to the surface of the base material, or sandwiched between the base materials.

Examples of the base material include resin, glass, etc., but resin is preferable. Various forms of the resin can be used, such as an adhesive, a sheet, a film, a binder resin, and a molded body. Alternatively, a combination of multiple forms may be used, such as having an adhesive on the sheet.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above may be adopted within a range that does not impair the effects of the present invention.

<Example>
EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

In the examples, the maximum absorption wavelength and gram extinction coefficient of diphenylethene-based compounds were determined using a Shimadzu spectrophotometer UV-3600iplus manufactured by Shimadzu Corporation using a toluene solution with a concentration of 0.01 g/L at an optical path length of 10 mm. It was measured using

In each example or comparative example, the decomposition temperature was determined using a thermal analyzer Rigaku ThermoPlus Evo2 under a nitrogen atmosphere at a heating rate of 10°C/min and a temperature range of room temperature to 800°C. ) was measured.

　得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
ＥＳＩ－Ｍａｓｓ：　３９９（Ｍ＋Ｈ）＋
５％重量減温度：３０２℃、吸熱温度ピークトップ：９６℃
　このようにして得られた化合物のトルエン溶液は３５４ｎｍに極大吸収を示し、グラム吸光係数は３．４３×１０４ｍＬ／ｇ・ｃｍであった。 (Example 1) Production of Compound Example 17 6.08 g of 4-(4-toluylthio)benzophenone (manufactured by TCI), 3.96 g of ethyl cyanoacetate, and 30 ml of methylene chloride were mixed and cooled to 0 to 5°C.
After 11.4 g of titanium tetrachloride and 12.1 g of N-methylmorpholine were added dropwise, the mixture was stirred for 2 hours. 100 ml each of water and chloroform were added to the reaction mixture, and the target product was extracted into the chloroform phase. The chloroform phase was concentrated under reduced pressure, 100 ml of methanol was added thereto, the precipitate was collected by filtration, washed with methanol, and dried with ventilation at 60°C to obtain 7.98 g of the desired yellow powder.

The obtained compound was confirmed to be the desired compound based on the analysis results described below.
ESI-Mass: 399 (M+H)+
5% weight loss temperature: 302℃, endothermic temperature peak top: 96℃
The toluene solution of the compound thus obtained showed maximum absorption at 354 nm, and the gram extinction coefficient was 3.43 x 104 mL/gcm.

　得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
ＥＳＩ－Ｍａｓｓ：　３５２（Ｍ＋Ｈ）＋
５％重量減温度：２７５℃、吸熱温度ピークトップ：１６９℃
　このようにして得られた化合物のトルエン溶液は３７８ｎｍに極大吸収を示し、グラム吸光係数は５．２４×１０４ｍＬ／ｇ・ｃｍであった。 (Example 2) Production of Compound Example 2 6.08 g of 4-(4-toluylthio)benzophenone (manufactured by TCI), 2.64 g of malononitrile, and 30 ml of methylene chloride were mixed and cooled to 0 to 5°C.
After 11.4 g of titanium tetrachloride and 12.1 g of N-methylmorpholine were added dropwise, the mixture was stirred for 2 hours. After the same post-treatment as in Example 1, 4.26 g of the desired yellow powder was obtained.

The obtained compound was confirmed to be the desired compound based on the analysis results described below.
ESI-Mass: 352 (M+H)+
5% weight loss temperature: 275℃, endothermic temperature peak top: 169℃
The toluene solution of the compound thus obtained showed maximum absorption at 378 nm, and had a gram extinction coefficient of 5.24×10 4 mL/g·cm.

　得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
ＥＳＩ－Ｍａｓｓ：　５２１（Ｍ＋Ｈ）＋
５％重量減温度：３４２℃、吸熱温度ピークトップ：１４９℃
　このようにして得られた化合物のトルエン溶液は３５６ｎｍに極大吸収を示し、グラム吸光係数４．６０×１０４ｍＬ／ｇ・ｃｍであった。 (Example 3) Production of Compound Example 22 10.0 g of dichlorobenzophenone, 9.89 g of p-toluenethiol, 16.5 g of potassium carbonate, and 100 ml of dimethylformamide were mixed and refluxed for 2 hours.
The product was dropped into 300 ml of water to obtain a precipitate. The precipitate was collected by filtration, washed with methanol, and dried under ventilation at 60°C.
4.26 g of dry matter, 1.98 g of ethyl cyanoacetate, and 30 ml of methylene chloride were mixed and cooled to 0 to 5°C. After 5.68 g of titanium tetrachloride and 6.06 g of N-methylmorpholine were added dropwise, the mixture was stirred for 2 hours. After the same post-treatment as in Example 1, 3.91 g of the desired yellow powder was obtained.

The obtained compound was confirmed to be the desired compound based on the analysis results described below.
ESI-Mass: 521 (M+H)+
5% weight loss temperature: 342℃, endothermic temperature peak top: 149℃
The toluene solution of the compound thus obtained exhibited maximum absorption at 356 nm, and had a gram extinction coefficient of 4.60×10 4 mL/g·cm.

　得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
ＥＳＩ－Ｍａｓｓ：　４７４（Ｍ＋Ｈ）＋
５％重量減温度：３４９℃、吸熱温度ピークトップ：１８９℃
　このようにして得られた化合物のトルエン溶液は３７５ｎｍに極大吸収を示し、グラム吸光係数は６．５１×１０４ｍＬ／ｇ・ｃｍであった。 (Example 4) Production of Compound Example 8 10.0 g of dichlorobenzophenone, 9.89 g of p-toluenethiol, 16.5 g of potassium carbonate, and 100 ml of dimethylformamide were mixed and refluxed for 2 hours.
The product was dropped into 300 ml of water to obtain a precipitate. The precipitate was collected by filtration, washed with methanol, and dried.
3.87 g of dry matter, 1.20 g of malononitrile, and 30 ml of methylene chloride were mixed and cooled to 0 to 5°C. After 11.4 g of titanium tetrachloride and 12.1 g of N-methylmorpholine were added dropwise, the mixture was stirred for 2 hours. After the same post-treatment as in Example 1, 3.2 g of the desired yellow powder was obtained.

The obtained compound was confirmed to be the desired compound based on the analysis results described below.
ESI-Mass: 474(M+H)+
5% weight loss temperature: 349℃, endothermic temperature peak top: 189℃
The toluene solution of the compound thus obtained showed maximum absorption at 375 nm, and the gram extinction coefficient was 6.51×10 4 mL/g·cm.

(Example 5)
Compound 26 was produced in the same manner as in Example 3, except that 4-fluorobenzenethiol was used instead of p-toluenethiol and 3,3,3,-trifluoropropanenitrile was used instead of ethyl cyanoacetate. did.

(Example 6)
Compound 35 was produced in the same manner as in Example 3, except that 1-butanethiol was used instead of p-toluenethiol and ethyl nitroacetate was used instead of ethyl cyanoacetate.

<Evaluation>
The following evaluations were performed for all Examples. Further, as comparative examples, similar evaluations were conducted using the following Comparative Compounds 1 to 6.

(Preparation of test sample)
2.5 g of a chloroform solution (6.6% by mass) of Delpet 80N (manufactured by Asahi Kasei Corporation) and 5 to 10 mg of the compounds obtained in Examples and Comparative Examples were mixed and dissolved to obtain a dye solution.
The dye solution was dropped onto a flat glass substrate with a thickness of 2 mm, and a film was formed by spinning at 1000 rpm for 20 seconds using a spin coater, and then dried under heating at 60° C. for 1 hour to prepare a test sample.

(absorption spectrum)
For each test sample of the compound obtained in the above example, the absorption spectrum of the resin film was measured using UV-3600iplus (manufactured by Shimadzu Corporation). Figure 1 shows the absorbance curves of each test sample.
As shown in FIG. 1, the diphenylethene compound according to the example had high absorbance in the range of 350 nm to 380 nm. In other words, it was suggested that the diphenylethene-based compounds according to Examples can reduce the transmittance of near-ultraviolet light.
From this, the diphenylethene-based compounds according to the examples can be suitably used as light absorbers, and the resin compositions containing the diphenylethene-based compounds and the optical components made of the resin compositions have a transmittance of near ultraviolet light. It was inferred that this could reduce the

(Light resistance test)
The above-mentioned test samples according to Examples and Comparative Examples were tested according to the relative spectral distribution specified in CIE85 Table 4 using a light resistance tester (manufactured by ATLAS) equipped with a daylight filter on a xenon lamp light source. The residual rate of the dye was evaluated until the cumulative irradiation time reached 200 hours.
The residual rate of the dye was calculated using the following formula.
Dye residual rate (%) = (Absorbance at maximum absorption wavelength before light irradiation) / (Absorbance at maximum absorption wavelength after light irradiation)
Table 1 shows the dye residual rates of Examples and Comparative Examples at a cumulative irradiation time of 200 hours.

As shown in Table 1, the diphenylethene compounds according to the examples exhibited a significantly higher dye residual rate than the compounds according to the comparative examples. In other words, it was suggested that the diphenylethene-based compounds of the present disclosure according to Examples are blue light-absorbing dyes with higher light resistance than the compounds of Comparative Examples.
From this, it was inferred that the resin composition containing the diphenylethene-based compound according to the example as a light absorbing agent and the optical component made of the resin composition had excellent stability in near-ultraviolet light absorption performance.
The irradiation time and dye residual rate are shown in FIG. 2. Note that the larger the value of the residual rate, the higher the light resistance of the dye.

The diphenylethene-based compound of the present disclosure can be used for optical articles such as eyeglass lenses, sun visors, shields for helmets, coats or films for display devices of information equipment. Further, the diphenylethene-based compound of the present disclosure can be used for the purpose of increasing the lifespan of image display devices such as liquid crystal display devices and organic EL displays, and improving contrast in bright rooms.

This application claims priority based on Japanese Patent Application No. 2022-106884 filed on July 1, 2022, and the entire disclosure thereof is incorporated herein.

Claims (8)

A diphenylethene compound represented by the following formula (I).

(In formula (I), R ₁ to R ₁₀ are each independently,
Hydrogen atom, halogen atom, cyano group, sulfone group,
substituted or unsubstituted alkyl group,
substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group,
substituted or unsubstituted aralkyl group,
substituted or unsubstituted aryl group,
substituted or unsubstituted alkylcarbonyl group,
substituted or unsubstituted arylcarbonyl group,
substituted or unsubstituted carboxylic acid ester group,
substituted or unsubstituted sulfonic acid ester group,
-SR, -OR, or -NRR'.
(In the formula, R and R' are each independently a hydrogen atom,
Substituted or unsubstituted alkyl group having 2 or more carbon atoms,
substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group,
Represents a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group. )
R ₁ to R ₁₀ may be bonded to each other to form an aliphatic ring or an aromatic ring.
However, at least one of R ₁ to R ₁₀ represents -SR.
R ₁₁ and R ₁₂ are each independently,
Halogen atom, cyano group, nitro group, formyl group, carboxy group, sulfone group,
substituted or unsubstituted alkyl group,
substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group,
substituted or unsubstituted aralkyl group,
substituted or unsubstituted aryl group,
substituted or unsubstituted alkylcarbonyl group,
substituted or unsubstituted arylcarbonyl group,
substituted or unsubstituted arylsulfonyl group,
Represents a substituted or unsubstituted carboxylic acid ester group or a substituted or unsubstituted sulfonic acid ester group.
R ₁₁ to R ₁₂ may be bonded to each other to form an aliphatic ring or an aromatic ring. ) The R ₁₁ and R ₁₂ are each independently,
Halogen atom, cyano group, nitro group, formyl group, carboxy group, sulfone group,
unsubstituted alkyl group substituted or unsubstituted aryl group,
substituted or unsubstituted halogenated alkyl group,
substituted or unsubstituted alkylcarbonyl group,
substituted or unsubstituted arylcarbonyl group,
substituted or unsubstituted arylsulfonyl group,
R ₁₁ to R ₁₂ represent a substituted or unsubstituted carboxylic acid ester group or a substituted or unsubstituted sulfonic acid ester group; may form a nitrogen heterocyclic aliphatic ring,
The diphenylethene compound according to claim 1. The above R ₁ to R ₁₀ are each independently,
hydrogen atom, hydroxyl group,
a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms,
a substituted or unsubstituted aralkyl group having 7 to 25 carbon atoms,
a substituted or unsubstituted aryl group having 6 to 24 carbon atoms,
a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms,
a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms,
represents a substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms,
However, at least one of R ₁ to R ₁₀ is
a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms,
The diphenylethene compound according to claim 1 or 2, which represents a substituted or unsubstituted aralkylthio group having 7 to 25 carbon atoms or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms. The diphenylethene compound according to claim 1, having a maximum absorption wavelength of 300 nm or more and 450 nm or less in a range of 300 nm or more and 800 nm or less. A light absorbent comprising the diphenylethene compound according to claim 1. A resin composition comprising the diphenylethene compound according to claim 1 and a resin. A cured product comprising the resin composition according to claim 6. An optical article comprising the cured product according to claim 7.

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